Photographic elements, compositions and processes

ABSTRACT

Sulfoxides having the formula of

United States Patent Herz PHOTOGRAPIIIC ELEMENTS, COMPOSITIONS AND PROCESSES Arthur H. Herz, Rochester, NY.

Eastman Kodak Company, Rochester, NY.

Filed: Apr. 29, 1974 Appl. No.: 465,037

Inventor:

Assignee:

US. Cl 96/11 45; 96/94 R; 96/1 14.7 Int. Cl. G03C 1/38 Field of Search 96/1 14.5, 114.7, 130, 127,

I References Cited UNITED STATES PATENTS 9/1973 Miller et a1. 96/94 R [451 Sept. 30, 1975 Primary E.\'aminerNorman G. Torchin Assistant E.\'aminerAlfonso T. Suro Pico Attorney, Agent, or Firml-l. E. Byers [57] ABSTRACT Sulfoxides having the formula of 22 Claims, N0 Drawings PHOTOGRAPHIC ELEMENTS, COMPOSITIONS AND PROCESSES BACKGROUND OF THE INVENTION This application concerns silver halide compositions containing sulfoxide surfactants and hydrophilic colloids and processes using the sulfoxide surfactants.

1n the preparation of a silver halide emulsion, it has been customary to add one or more surfactants to the emulsion so that the emulsion coats readily on film or paper supports. However, since silver halide emulsions are subject to fogging or to reactions of various ad denda, there has been a problem of obtaining surfactants which would be compatible with the colloid used in the emulsion as well as with the silver halide and other addenda. Saponin which has been a customary surfactant or coating aid, is a glucoside obtained from soapwart. Since it is a naturally occurring product, it varies in composition and it has been desirable to find a synthetic substance which could be substituted for saponin in photographic emulsions which would be uniform in composition and which would be subject to manufacturing control as to quality, composition and the like.

For a compound to be of practical use as a coating aid or as a surfactant in silver halide emulsion, it must not only wet the support as well as the surfaces of hoppers, slides and coating heads with the liquid emulsion, it must also exhibit no objectional effects on the stability, sensitivity and developability of the silver halide with which it remains in contact; Few wetting agents will fill the last requirements. Thus, anionic surfactants tend to form sparingly soluble salts with cationic organic additives such as cyanine dyes and may, therefore, interfere with spectral sensitization.

Cationic and zwitterionic wetting agents and non ionic surfactants derived from methylene oxide are known to decrease emulsion stability and to cause formation of storage fog (Piper, US. Pat. No. 2,886,437, Column 5, line 3). Similarly, although trialkylamine oxides are good wetting agents and coating aids (Henn, US. Pat. No. 2,490,760), these oxides display high emulsion activity; they can sensitize silver halide systems (Sprung, US. Pat. No. 3,113,026) and also tend to cause severe fog on development and storage.

Consideration must also be given to the effect which a wetting agent may exert on the development process. For instance, it is known that certain sulfoxides, e.g. dimethyl or diphenylsulfoxide (Belgium Pat. No. 688,917, Dupont) increase developability when added at high concentrations to hydroquinone or Elonhydroquinone developer solutions.

DESCRIPTION OF THE PRIOR ART Amine oxides are known as addenda for photographic emulsions such as those disclosed in Elins et al, US. Pat. NO. 3,698,901, issued Oct. 17, 1972. However, amine oxides fog the emulsion.

SUMMARY OF THE INVENTION According to the invention, sulfoxides having the formula in which R, is alkyl having 8 18 carbon atoms, aryl having 6 14 carbon atoms, or aralkyl having 7 16 carbon atoms and R is alkyl having 1 14 carbon atoms, aryl having 6 14 carbon atoms or aralkyl having 7 16 carbon atoms, and R plus R contain more than 8 carbon atoms, are useful as surfactants in silver halide emulsions comprising a hydrophilic colloid such as gelatin, since they can be used without fogging the silver halide emulsion.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A wide range of sulfoxides can be used within the scope of the invention providing that the sulfoxide has the formula in which R is alkyl having 8 18 carbon atoms, aryl having 6 14 carbon atoms, or aralkyl having 7 16 carbon atoms and R is alkyl having 1 14 carbon atoms, aryl having 6 14 carbon atoms or aralkyl having 7 16 carbon atoms, and R plus R contain more than 8 carbon atoms. It will be appreciated that R and R may be further substituted with non-ionic moieties such as halide, hydroxy, ether, nitrile, amide, ester or other carbonyl groups.

These monomeric sulfoxides are surface active; ie. they decrease the interfacial tension between two liquidsor the surface tension at the water/air interface. They exhibit little if any influence on storage stability of highly sensitive silver halide emulsions. These sulfoxides according to our invention exhibit essentially no influence on development of Elon -hydroquinone developers. However, they tend to restrain strongly development by hydroquinone developing solution. This effect has been successfully applied to improve the quality of lith-type emulsions which are processed in a hydroquinone developer resulting in improved'dot quality. Lith emulsions typically are silver halide emulsions in which the silver halide comprises at least 50 percent by weight silver chloride and preferably at least percent. All the compounds useful in my invention are non-ionic, water-soluble and surface-active. It will be appreciated that the concentration range may vary considerably but a particularly useful range is from 2mg to about l'0/l00g of vehicle.

Trademark for p-methyl aminophenol sulfate.

Useful sulfoxides include the following:

hydroxyethyl octyl sulfoxide dodecyl methyl sulfoxide phenyl sulfoxidc decamethylenc bismethyl sulfoxide bcnzyl sulfoxidc p-chlorophcnyl sulfoxide SO o-hydroxyphenyl OH Ho sulfoxldc CH O-SOOCH tolyl sulfoxidc so m-aminophcnyl sulfoxide NH NH CH -@$O-QCH xylyl sulfoxide c 3 CH3 CH -Continued phenyl sulfuxime The vehicle may be a hydrophilic colloid suitable for use in radiation-sensitive silver halide emulsions. Hydrophilic colloids which may be used include the naturally-occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like.

Photographic silver halide emulsions, preparations, addenda, processing and systems which can be used are disclosed in Product Licensing Index, Vol. 92, December, 1971, publication 9232, pages 107 110, paragraphs 1 IX and XIII XXV with hydrophilic coatings other than those which are radiationscnsitive including paper coatings having therein pigments such as clay, titanium dioxide, and the like.

The following examples are included for a further understanding of the invention:

-EXAMPLE 1 A high-speed, gold and sulfur sensitized silver bromoiodidephotographic emulsion containing the addenda described below is coated on film support and contains per square meter about 4.3 grams of silver and about 9.7 grams of gelatin. Before coating, the compounds are added to the liquid emulsion at pH 6.4 at the indicated concentration. In addition, the emulsion contains 0.15 millimole/mole of silver of a spectral sensitizing dye, 5,5 '-6,6'-tetrachlor0-3,3'-diethyl-1,1 '-dioctadecyl benzimidazolo-carbocyanine p-tolu'enesulfonate. Samples of the emulsions are exposed through appropriate 'filters to obtain values for blue speed and for minus blue speed; Development is carried out with Kodak Developer D-l9 for 4 minutes at 20C.

(2 )Kodak Developer D- l 9 Water (about 50C) 2.0 liters N-methyl-p-aminophenol sulfate 8.8 grams Sodium Sulfite,

desiccated 384.0 grams 'Hydroquinone 35 .0 grams Sodium Carbonate,

desiccated 192.0 grams Potassium Bromide 20.0 grams Cold Water to make 4.0 liters The results show that while a simple sulfoXide had no substantial effect on silver halide sensitivity, the compounds of this invention strongly enhanced the activity of a sparingly soluble spectral sensitizer with reduced deleterious influence on intrinsic (blue) sensitivity.

TABLE I-Continued er) Sulfoxide concentration in g/g Minus millimoles per mole AgX colloid Blue Blue C, H -,SOCH 25 millimoles 2.4 100 33.0

C H -SOC H ,OH 25 millimoles 2.1 7.4

"Speed is expressed as a reciprocal of exposure on an Eastman 1B Sensitometer and is measured at 0.3 density units above fog. The original test of the control is assigned a relative speed of 100.

*C'ontains saponin. 3g/mole silver EXAMPLE 2 The following sulfoxides are incorporated in gelatin:

hydroxye thyl octyl sulfoxide hydroxyhutyl octyl sulfoxide 3 CH3 so cH.,, methyl tolyl sulfoxide Tables 11 and III contain the surface tensions and stainless steel spread values in gelatin solutions at pH about 5 of 7 percent gelatin (lime-processed) and 13.3 percent gelatin (acid processed).

TABLE 11 Surface Tensions (dynes/cm) of Various Sulfoxides in 7% Lime Processed and 13.3% Acid Processed Gelatin Gelatin Sulfoxide Conc. Com- Com- Compound pound pound Solution g/lOOg Gelatin No. 1 No. 2 No. 3

TABLE III Stainless Steel Spread Values (cm for Various Sulfoxides in 7% Lime Processed and 13.3% Acid Processed Gelatin The stainless steel spread values (SSS) indicate the extent to which a surfactant enhances the ability of gelatin solutions to wet the stainless steel hopper slides used in hopper coating operations. They are determined by delivering, in a standard manner from a pipette, 1 ml of the gelatin solutions containing the surfactant at various concentrations (0.0 to 1.57 g/ 100g of gelatin), to the surface of a highly polished stainless steel plate and measuring the area spontaneously covered. This area is reported in cm for each surfactant concentration. The higher the values, the more like is the ability of the surfactant to reduce the incidence of EXAMPLE 4 A high speed, gold and sulfur sensitized silver bromoiodide photographic emulsion containing the addenda described below was coated on film support and conpencil line streaks arising from slide contamination in 5 pp coating Operatic taming per square meter ea. 4.3g Ag and 9.7 g gelatin. It is apparent from the results that whereas the pre- Bfore f the compounds were W to the hq' ferred compounds of this invention, e.g., Nos. 1 and 2, uld emulslon at pH and pBr 3 at the mdcated condeerease the surface tension at the air/gelatin solution cemmnogsj The coatmgs i exiiosed l) interface and increase SSS values, the sulfoxide No. 3 1O processe m the .mdwlted Kodl Deve Oper at 20 which is not surfaceactive was without substantial effeet.

TABLE V EXAMPLE 3 A high speed, gold and sulfur sensitized silver bromol5 Cone (3) 4 Smmgem iodide photographic emulsion containing the addenda per "mic x Specd y Fog Fog described below was coated on film support and con- Control I00 [.0 .04 .04 taming per square meter about 4.3 g Ag and 9.7 g gela CIZHZS NO (CH3)Z m 23 079 32 .32 tin. Before coating, the compounds were added to the C,. ,H25 NO. (CHH) 3Q 30 0,82 '33 ,40 liquid emulsion at pH 6.4 at the indicated concentra- 20 2 3 '2823 3 P, race .0 tlOllS. The dry coatings were exposed and processed in s0 3m 1 1'02 m 04 the indicated Kodak Developers at C. CH..-s0 C1-1 930 132 0.96 .04 .04

The data of Tables IV and V make it apparent that "S d d i 1 pee is expresse as a reciprocal ol'exposure oi a E:.'t "3 S- ."t 't' the urfdceaCt/e sulfoxides, contrast to the related and is measured at 0.3 density units ahove fog. Th e oi igin ail i d s i of amine oxides and phosphine oxides, do not induce fog f z i l Z Q 2" .0: .49'. or storage instability in highly sensitive emulsions. They W exhibit no deleterious effects in conventional developers like Kodak Developer D-l9 but in contrast to simple sulfoxides like dimethyl sulfoxide, the surface ac- EXAMPLE 5 tive sulfoxides restrain development in hydroquinone developing solutions such as Kodak Developer D-85 (5) Monoxides as Development Modifiers in Lith Systems and restram development AS hlghly alkaline A high contrast, silver chlorobromoiodide gelatin condmons (Kodak Developer 13-8 emulsion comprising 90 mole percent of chloride, 9 is mole percent bromide and 1 mole percent iodide was prepared containing the sulfoxidc of poly-2,2- (m DEVELOPER D (thiodiethylcne glutai'ate). After exposure, the coatings Water about F (30c) 500 cc were processed for the indicated minutes in Kodak De- Sodium Sulfite desiccated 30.0 grams Paraformaldehyde 7.5 grams Veloper 13-85- Sodium Bisulfite 2.2 grams 4O Boric Acid Crystals 7.5 grams Hydroquinone 22.5 grams TABLE VI Potassium Bromide L6 grams Water to make 1.0 liter GKODAK DEVELOPER 13-8 4% min. Development Time 750 milliliters Polymeric Sulfoxide in g/lOOg Dot (Anhydrous) mg/mole Ag gelatin Speed Contrast Quality Sodium Hydroxide (Granular) 37.5 grams Potassium Bromide (Anhydrous) 30.0 grams mg (Control) 0 01 l Water to make l.0 liter mg 50 mg 0.02 1 18 5.6 1 mg 004 I48 7.0 s 50 400 mg 0.16 89 l3.0 8 Table Vl demonstrates that this development restraint towards hydroquinone in Lith-type emulsions is also induced b o] meric sulfoxides and leads to a de- The invention has been described in detail with ary P Y p sirable loss of toe s eed and both enhanced contrast ticular reference to referred embodiments thereof,

P P and Dot Quality. 5; but it will be understood that variations and modifica- TABLE IV 4 min. D-l9 4 min. HQ 2 min. D-8 g/lOOg g/mole Storage Compound gelatin Ag Speed" Fog Fog Speed" Fog Speed Fog Control 0 lOO .08 .16 100 .06 I00 .12 C H- SOCH;; .94 2.3 95 .08 .13 58 .05 67 .ll

CH -SOCH .74 1.8 .07 .14 5s .05 94 .12

"Speed is expressed as a reciprocal of exposure on an Eastman lB Sensitomeler and is measured at 0.3 density units uhove fog. The original test of the control is assigned a relative speed of 100. "'Storage for l Week at 50% RH. l20F ""Composition of D-l9 but with methyl-p-aminnphenol sulfate omitted: hence. a pure hydroquinone developer at pH l0.4.

tions can be effected within the spirit and scope of the invention.

1 claim:

1. An unexposed radiation-sensitive silver halide emulsion containing a hydrophilic colloid and a sulfoxide having the formula in which R is alkyl having 8 18 carbon atoms, aryl having 6 14 carbon atoms, or aralkyl having 7 16 carbon atoms and R is alkyl having 1 14 carbon atoms, aryl having 6 14 carbon atoms or aralkyl having 7 16 carbon atoms and R plus R contain more than 8 carbon atoms.

2. An emulsion of claim 1 which contains a spectral sensitizing dye.

3. An emulsion of claim 1 which contains about 2mg to about 10g of said sulfoxide per 100g of colloid.

4. A lith emulsion of claim 1 in which said silver halide comprises at least 50 percent chloride.

5. An emulsion of claim 1 in which said sulfoxide is hydroxyethyl octyl sulfoxide.

6. An emulsion of claim 1 in which said sulfoxide is hydroxybutyl octyl sulfoxide.

7. An emulsion of claim 1 in which said sulfoxide is hydroxyethyl dodecyl sulfoxide.

8. An emulsion of claim 1 in which said sulfoxide is methyl dodecyl sulfoxide.

9. A photographic element comprising a support having thereon an unexposed radiation sensitive gelatin silver halide emulsion containing a hydrophilic colloid and a sulfoxide having the formula I R SOR in which R is alkyl having 8 18 carbon atoms, aryl having 6 14 carbon atoms, or aralkyl having '7 16 carbon atoms'and R 'is alkyl having 1 14 carbon atoms. aryl having 6 14 carbon atoms or aralkyl having 7 16 carbon atoms and R plus R contain more than 8 carbon atoms.

10. An element of claim 5 which contains a spectral sensitizing dye.

12. An element of claim 5 which contains about 2mg to about 10g of said sulfoxide per g of colloid.

13. An element of claim 5 in which said silver halide comprises at least 50 percent chloride.

14. In a process of coating a radiation-sensitive silver halide emulsion comprising a hydrophilic colloid the improvement comprising adding to said emulsion a sulfoxide having the formula in which R, is alkyl having 8 18 carbon atoms, aryl having 6 14 carbon atoms, or aralkyl having 7 16 carbon atoms and R is alkyl having 1 14 carbon atoms, aryl having 6 14 carbon atoms or aralkyl having 7 16 carbon atoms and R plus R contain more than 8 carbon atoms. I

15. A process of claim 14 in which said emulsion contains a spectral sensitizing dye.

16. A process of claim 14 in which said colloid is gel atin.

17. A process of claim 14 in which said emulsion contains about 2 mg to about 10 g of said sulfoxide per 100 g of colloid.

18. A process of claim 14 in which said silver halide comprises at least 50 percent chloride.

19. An unexposed radiation sensitive gelatin silver halide emulsion containing a sulfoxide having the formula in which R is alkyl having 8-18 carbon atoms, aryl having 6l4 carbon atoms, or aralkyl having 7-16 carbon atoms and R is alkyl'having l-l4 carbon atoms, aryl having 6l4 carbon atoms or aralkyl having 7+l6 carbon atoms and R, plus R contain more than 8 carbon atoms.

20. An emulsion of. claim 19 in which said emulsion contains a spectral sensitizing dye.

21. An emulsion of claim 19 in which said emulsion contains about 2 mg to about 10 g of said sulfoxide per 100 g of gelatin.

22. An emulsion of claim 19 in which saidsilver halide comprises at least 50 percent chloride. 

1. AN UNEXPOSED RADIATION SENSATIVE SILVER HALIDE EMULSUON KCONTAINING AHYDROPHLIC COLLOID AND A SULFOXIDE HAVING THE FORMULA
 2. An emulsion of claim 1 which contains a spectral sensitizing dye.
 3. An emulsion of claim 1 which contains about 2mg to about 10g of said sulfoxide per 100g of colloid.
 4. A lith emulsion of claim 1 in which said silver halide comprises at least 50 percent chloride.
 5. An emulsion of claim 1 in which said sulfoxide is hydroxyethyl octyl sulfoxide.
 6. An emulsion of claim 1 in which said sulfoxide is hydroxybutyl octyl sulfoxide.
 7. An emulsion of claim 1 in which said sulfoxide is hydroxyethyl dodecyl sulfoxide.
 8. An emulsion of claim 1 in which said sulfoxide is methyl dodecyl sulfoxide.
 9. A photographic element comprising a support having thereon an unexposed radiation sensitive gelatin silver halide emulsion containing a hydrophilic colloid and a sulfoxide having the formula R1-SO-R2 in which R1 is alkyl having 8 - 18 carbon atoms, aryl having 6 -14 carbon atoms, or aralkyl having 7 - 16 carbon atoms and R2 is alkyl having 1 - 14 carbon atoms, aryl having 6 - 14 carbon atoms or aralkyl having 7 - 16 carbon atoms and R1 plus R2 contain more than 8 carbon atoms.
 10. An element of claim 5 which contains a spectral sensitizing dye.
 11. An element of claim 5 in which said colloid is gelatin.
 12. An element of claim 5 which contains about 2mg to about 10g of said sulfoxide per 100g of colloid.
 13. An element of claim 5 in which said silver halide comprises at least 50 percent chloride.
 14. In a process of coating a radiation-sensitive silver halide emulsion comprising a hydrophilic colloid the improvement comprising adding to said emulsion a sulfoxide having the formula R1-SO-R2 in which R1 is alkyl having 8 - 18 carbon atoms, aryl having 6 -14 carbon atoms, or aralkyl having 7 - 16 carbon atoms and R2 is alkyl having 1 - 14 carbon atoms, aryl having 6 - 14 carbon atoms or aralkyl having 7 - 16 carbon atoms and R1 plus R2 contain more than 8 carbon atoms.
 15. A process of claim 14 in which said emulsion contains a spectral sensitizing dye.
 16. A process of claim 14 in which said colloid is gelatin.
 17. A process of claim 14 in which said emulsion contains about 2 mg to about 10 g of said sulfoxide per 100 g of colloid.
 18. A process of claim 14 in which said silver halide comprises at least 50 percent chloride.
 19. An unexposed radiation sensitive gelatin silver halide emulsion containing a sulfoxide having the formula R1 - SO - R2 in which R1 is alkyl having 8-18 carbon atoms, aryl having 6-14 carbon atoms, or aralkyl having 7-16 carbon atoms and R2 is alkyl having 1-14 carbon atoms, aryl having 6-14 carbon atoms or aralkyl having 7-16 carbon atoms and R1 plus R2 contain more than 8 carbon atoms.
 20. An emulsion of claim 19 in which said emulsion contains a spectral sensitizing dye.
 21. An emulsion of claim 19 in which said emulsion contains about 2 mg to about 10 g of said sulfoxide per 100 g of gelatin.
 22. An emulsion of claim 19 in which said silver halide comprises at least 50 percent chloride. 